Pigment ink formulations for dod inkjet printing of textile fabrics

Abstract

The present invention relates to a silicone-free and fluorine-free water-based pigment piezoelectric drop-on-demand inkjet ink formulation for textile printing and a method of manufacturing printed textile fabrics using the formulation.

Description

Technical Field

[0001] The technical field of this invention is pigment ink formulations for piezoelectric drop-on-demand (DOD) inkjet printing of textile fabrics and methods for manufacturing printed textile fabrics by piezoelectric DOD inkjet printing. Background Technology

[0002] Screen printing and roller printing methods are widely used in the textile industry to print images such as text, pictures, or designs onto textile fabrics (e.g., woven, knitted, and nonwoven fabrics). Recently, inkjet printing methods have emerged as an attractive alternative to known textile printing methods because they enable computer-based image processing and allow textile printing to be performed in a virtually plateless manner.

[0003] When inkjet inks contain pigments used as colorants, it is necessary to add a fixing resin to the ink to fix the pigments onto the textile fabric. To improve rubbing fastness, inks typically contain a high resin content, which leads to an alteration in the hand feel of the textile.

[0004] For example, US 2014 / 0210900 A1 describes an ink assembly for piezoelectric DOD inkjet textile printing, comprising a first ink having pigment and resin; and a second ink having a mixture of pigment, resin, and a specific emulsifier. The first ink is used to form a base layer, and the second ink is attached to this base layer on the fabric. The resin used in the ink is a water-dispersible polyurethane-based resin having a Tg below 0°C. This textile printing method involves a pretreatment process for applying a pretreatment agent containing a coagulant, which reacts with the components of the ink arriving at the fabric to form a first image by attaching the first ink to the fabric; and using the second ink to form a second image by attaching the second ink to the first image. Although the ink appears compatible with a wide variety of textile fabrics, this inkjet printing method is time-consuming (including two printing steps for attaching the first ink to the fabric and the second ink to the image formed with the first ink) and requires a pretreatment step of applying the pretreatment agent to the fabric prior to the first printing step.

[0005] US 2019 / 0352528 A1 describes a water-based pigment ink for inkjet printing on textiles with improved rubbing fastness. To improve rubbing fastness, a specific combination of a first water-dispersible resin and a water-dispersible polystyrene resin (a second water-dispersible resin) is used in specific weight percentages and weight ratios. The first water-dispersible resin is a water-dispersible polyurethane resin, a water-dispersible (meth)acrylic resin, or a water-dispersible styrene / (meth)acrylic resin. The total amount of the first and second water-dispersible resins is 7.2 to 15% by weight, based on the total mass of the ink, and the amount of the first water-dispersible resin is 3 to 6% by weight, based on the total mass of the ink. To ensure good color development, the textile fabric must undergo a pretreatment step using a pretreatment agent comprising a cationic polymer or a polyvalent metal salt and a water-dispersible resin. The printing process of US 2019 / 0352528 A1 appears to be more convenient than the previously described method. However, it also requires a pretreatment step before inkjet printing and seems to be limited to polystyrene substrates.

[0006] Alternative techniques proposed to improve rubbing fastness include a method of protecting printed images by coating the image with a resin layer without colorants as a topcoat. These techniques also result in alterations to the hand feel of the printed textile fabric and require additional coating steps.

[0007] Therefore, there remains a need for pigment-based DOD inkjet ink formulations and DOD printing methods for textile fabrics that address the aforementioned shortcomings. In particular, there is a need for DOD inkjet formulations that are universally applicable to textile fabric substrates, eliminate the need for additional time-consuming pretreatment steps before printing or coating steps after printing, and provide printed textile fabrics with excellent rubbing fastness and color development without affecting the hand feel of the textiles. Summary of the Invention

[0008] Overview of the Invention

[0009] Therefore, the object of the present invention is to provide a water-based piezoelectric drop-on-demand (DOD) inkjet ink formulation for textile printing, wherein the formulation comprises the following:

[0010] - 3% to 15.0% by weight of pigment dispersed in the formulation;

[0011] - Water-dispersible (meth)acrylic resins;

[0012] - Water-dispersible styrene-(meth)acrylic resins;

[0013] - Water-dispersible polyurethane resin;

[0014] - Up to 2% by weight of surfactant;

[0015] - 20% to 40% by weight of 1,2,3-propanetriol;

[0016] - Optionally, one or more of a pH adjuster, biocide, thickener, and other water-miscible solvent; and

[0017] - water;

[0018] in,

[0019] At least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin has a glass transition temperature (Tg) of less than 140°C and greater than or equal to 20°C.

[0020] At least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin has a glass transition temperature (Tg) below 20°C; and

[0021] The total amount of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin and the water-dispersible polyurethane resin is 7% to 10% by weight.

[0022] The percentage by weight is based on the total weight of the composition. This ink formulation is prepared at 25°C and for 200-400 seconds. -1 It has a viscosity of 4 cP (mPa·s) to 9 cP (mPa·s), preferably 4-7 cP (mPa·s), at a shear rate. Advantageously, the DOD inkjet ink formulation is silicone-free and fluorine-free.

[0023] According to another aspect of the invention, there is a method for manufacturing optionally finished textile fabrics for printing. The method comprises the following steps, preferably:

[0024] a) Provide an uncolored textile fabric, wherein the fabric has not previously undergone pretreatment for inkjet printing;

[0025] b) Print one or more inkjet formulations on one side of the fabric or on one or more areas of the fabric using piezoelectric on-demand inkjet printing, wherein at least one of the inkjet formulations is an inkjet ink formulation according to the present invention.

[0026] c) Optionally, piezoelectric on-demand inkjet printing of one or more inkjet formulations is performed on the other side of the fabric or on one or more areas of the other side, wherein at least one of the inkjet formulations is an inkjet ink formulation according to the invention.

[0027] d) Drying the textile by exposing it to air at a temperature of about 120°C to about 140°C to provide a dried textile; and

[0028] e) Calender the textile fabric at a temperature of about 140°C to about 180°C for at least 10 seconds to provide an optional finished textile fabric for printing.

[0029] According to another aspect of the invention, there is a method for manufacturing garments using the optionally finished textile fabric printed with this material.

[0030] Detailed Description of the Invention

[0031] Therefore, the object of the present invention is to address the need for pigment-based DOD inkjet ink formulations that are universally applicable to textile fabric substrates, require no additional time-consuming pretreatment and / or post-coating steps, and provide printed textile fabrics with excellent rubbing fastness and color development properties without altering the hand feel of the textiles; and the need for a time-saving and environmentally friendly manufacturing method using such ink formulations. This object is achieved by the water-based piezoelectric drop-on-demand (DOD) ink formulation according to claim 1 and the manufacturing method according to claims 7 and 15. Preferred embodiments are disclosed in the specification and dependent claims.

[0032] The invention will now be described in more detail.

[0033] When this specification refers to "preferred" embodiments / features, combinations of such "preferred" embodiments / features are also considered to be disclosed, provided that a particular combination of "preferred" embodiments / features is technically meaningful.

[0034] Unless otherwise stated, the following definitions apply to this specification:

[0035] As used herein, the terms “a,” “an,” “the,” and similar terms used in the context of this invention (especially in the context of the claims) are to be interpreted as encompassing both the singular and the plural, unless otherwise stated herein or clearly contradicted by the context.

[0036] As used herein, the term "and / or" means that all or only one element of the elements of the group may be present. For example, "A and / or B" means "A only, or B only, or both A and B". In the case of "A only", the term also covers the possibility that B is not present, i.e., "A only, but no B".

[0037] As used herein, the terms “including,” “containing,” and “comprising” are used in their open-ended, non-limiting sense. It should be understood that various embodiments, preferences, and scopes can be combined arbitrarily. Thus, for example, a solution containing compound A may contain other compounds besides A. However, the term “comprising” as in its particular embodiment also covers the more restrictive meanings of “essentially composed of” and “composed of,” thereby, for example, a “solution containing A, B, and optionally C” may also consist (essentially) of A and B, or (essentially) of A, B, and C. As used herein, the transitional phrase “essentially composed of” (and grammatical variations) is to be interpreted as covering the described materials or steps and those that do not materially affect the essential and novel features of the claimed invention. Therefore, the term “essentially composed of” should not be interpreted as equivalent to “comprising.”

[0038] As used herein, the term "about" means that the quantity or value under discussion can be a specific value or some other value adjacent to it. Generally, the term "about" indicating a value is intended to represent a range within ±5% of that value. As an example, the phrase "about 100" represents a range of 100 ± 5, that is, a range from 95 to 105. Preferably, the range indicated by the term "about" represents a range within ±3%, more preferably ±1%, of that value. Generally, when the term "about" is used, similar results or effects according to the invention are expected to be obtained within ±5% of the indicated value.

[0039] Inkjet ink formulation

[0040] Surprisingly, a substance has been discovered that operates at 25°C and for 200-400 seconds. -1 A silicone-free and fluorine-free formulation having a viscosity of 4 cP (mPa·s) to 9 cP (mPa·s), preferably 4-7 cP (mPa·s), at a shear rate, and comprising the following:

[0041] - 3% to 15.0% by weight of pigment dispersed in the formulation;

[0042] - Water-dispersible (meth)acrylic resins;

[0043] - Water-dispersible styrene-(meth)acrylic resins;

[0044] - Water-dispersible polyurethane resin;

[0045] - Up to 2% by weight of surfactant;

[0046] - 20% to 40% by weight of 1,2,3-propanetriol;

[0047] - Optionally, at least one of a pH adjuster, a biocide, a thickener, and another water-miscible solvent; and

[0048] - water;

[0049] in,

[0050] At least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin has a glass transition temperature (Tg) of less than 140°C and greater than or equal to 20°C.

[0051] At least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin has a glass transition temperature (Tg) below 20°C; and

[0052] The total amount of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin is 7% to 10% by weight. This formulation is particularly suitable for textile printing on various textile fabric substrates via piezoelectric DOD inkjet printing, eliminating the need for additional time-consuming pretreatment and / or post-coating steps, and providing printed textile fabrics with excellent rubbing fastness and color development properties without altering the hand feel of the textile. Advantageously, this formulation does not contain known non-biodegradable and even toxic organosilicon and fluorinated compounds. Unless otherwise specified, weight percent is based on the total weight of the formulation.

[0053] The term "silicone-free composition" refers to a composition that does not contain silicone / polysiloxane. As used herein, the terms "silicone" and "polysiloxane" cover all polymers containing a polysiloxane structural moiety, including but not limited to silicone / polysiloxane oils, modified polysiloxanes such as epoxy- and / or amino-modified polysiloxanes, polyether-modified polysiloxanes, and linear multiblock polysiloxane copolymers.

[0054] The term "fluorine-free composition" refers to a composition that does not contain fluorinated compounds such as perfluorinated or polyfluoroalkyl substances (PFAS).

[0055] To ensure compatibility with commercially available piezoelectric DOD inkjet printers, the piezoelectric DOD inkjet ink formulation must be prepared at 25°C for 200-400 seconds. -1 It has a viscosity of 4 cP (mPa·s) to 9 cP (mPa·s), preferably 4-7 cP (mPa·s), at a shear rate. This viscosity can be measured using a BROOKFLIED DVN viscometer, flat cone, 50 RPM.

[0056] This piezoelectric DOD inkjet ink formulation contains 3%-15.0% by weight, preferably 3%-10.0% by weight, more preferably 3%-6% by weight, and very preferably 3%-4.5% by weight of pigment dispersed within the formulation. Due to their composition (the combination of specific water-dispersible resins and solvents in the stated amounts), the inks described herein provide strong color coverage on the printed surface even at low pigment contents such as 3%-6% by weight or 3%-4.5% by weight, with little or no backside staining.

[0057] To avoid printhead clogging, the pigments contained in the ink are characterized by a particle size D95 of 0.2 μm–0.3 μm as measured by dynamic light scattering diffraction particle size analysis.

[0058] Any pigment commonly used in this technical field can be used as this pigment. Examples of pigments include organic pigments such as azo pigments, phthalocyanine pigments, dye pigments, fused polycyclic pigments, nitro pigments, and nitroso pigments; inorganic pigments, including metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, and nickel, as well as metal oxides and sulfides; and yellow ochre, ultramarine, and iron blue pigments; and carbon black such as furnace black, lampblack, acetylene black, and channel black. Examples of commercially available pigments suitable for use in this formulation include Pigment Black 7 (carbon black), Pigment Yellow (PY) 155, Pigment Red (PR) 254, Pigment Blue (PB) 15:3, Pigment Blue (PV) 23, Pigment Red (PV) 19, Pigment Red (PR) 122, Pigment Red (PV) 19, Pigment Red (PR) 254, Pigment Yellow (PY) 155, Pigment Orange (PO) 34, and Pigment Blue (PV) 23.

[0059] The piezoelectric DOD inkjet ink formulation further comprises a water-dispersible styrene-(meth)acrylate resin, a water-dispersible (meth)acrylate resin, and a water-dispersible polyurethane resin. The combination of this water-dispersible (meth)acrylate resin, this water-dispersible styrene-(meth)acrylate resin, and this water-dispersible polyurethane resin, having the glass transition temperatures described herein, provides improved wet and dry rubbing fastness, improved color development, and lower back staining compared to individual water-dispersible resins.

[0060] As used herein, the term "water-dispersible resin" includes self-emulsifying resins in which hydrophilic components necessary for stable dispersion in water are introduced, or resins that become water-dispersible through the use of external emulsifiers.

[0061] As used herein, the term "water-dispersible (meth)acrylic resin" includes a single water-dispersible (meth)acrylic resin and a combination of two or more (meth)acrylic resins.

[0062] The water-dispersible (meth)acrylate resin comprises at least methacrylate units derived from (meth)acrylate-based monomers and / or acrylic units derived from acrylic-based monomers. The water-dispersible (meth)acrylate resin may also comprise one or more other units, provided that these other units do not comprise styrene units derived from styrene monomers described below. Examples of (meth)acrylate-based and acrylic-based monomers include (meth)acrylates such as methyl (meth)acrylate and (meth)acrylic acid. The term "(meth)acrylate" means both "acrylic" and "methacrylate," and the term "(meth)acrylate" means both "acrylate" and "methacrylate."

[0063] As used herein, the term "water-dispersible styrene-(meth)acrylic resin" includes a single water-dispersible styrene-(meth)acrylic resin and a combination of two or more water-dispersible styrene-(meth)acrylic resins.

[0064] Water-dispersible styrene / (meth)acrylic resins comprise at least styrene units derived from styrene monomers, and methacrylic units derived from methacrylic monomers and / or acrylic units derived from acrylic monomers. Examples of styrene monomers include styrene and alkyl-modified styrene (e.g., α-methylstyrene).

[0065] Examples of commercially available water-dispersible (meth)acrylic resins and water-dispersible styrene / (meth)acrylic resins include Mowinyl 675ID (Tg: -32°C), Mowinyl 6960 (Tg: -32°C), Mowinyl 6963 (Tg: -28°C), Mowinyl 702 (Tg: -19°C), Mowinyl 8020 (Tg: -22°C), Mowinyl 966A (Tg: -29°C), Mowinyl 6718 (Tg: 3°C), Mowinyl 6750 (Tg: 0°C), and Mowinyl 7720 (Tg: 4°C), all manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and Joncryl PDX-7341 (Tg: 15°C), Joncryl, all manufactured by BASF Corporation. PDX-7370 (Tg: 12°C) and Joncryl® HPD 296KOH (Tg: 15°C), NeoCryl A-1094 (Tg: 21°C) and NeoCryl BT-62 (Tg: 22°C) manufactured by DSM Coating Resins DV, and Hycar manufactured by Lubrizol ® 26907 (Tg: 22℃) and Carboset 527 (Tg: 54℃) manufactured by Lubrizol.

[0066] As used herein, the term "water-dispersible polyurethane resin" includes a single water-dispersible polyurethane resin and a combination of two or more water-dispersible resins. Water-dispersible polyurethane resins have a urethane backbone. Examples of resins that can be used as water-dispersible polyurethane resins include polyether polyurethane resins containing ether bonds in addition to urethane bonds in the main chain, polyester polyurethane resins containing ester bonds in addition to urethane bonds in the main chain, and polycarbonate polyurethane resins containing carbonate bonds in addition to urethane bonds in the main chain. Among these, polycarbonate polyurethane resins and polyester polyurethane resins can be used particularly advantageously. Combinations of various types of water-dispersible polyurethane resins can also be used.

[0067] Preferred examples of water-dispersible polyurethane resins include anionic polyurethane resins having anionic functional groups such as carboxyl, sulfonyl, or hydroxyl groups.

[0068] Specific examples of water-dispersible polyurethane resins include SUPERFLEX 300 (Tg: -42°C), SUPERFLEX 420 (Tg: -10°C), SUPERFLEX 460 (Tg: -21°C), SUPERFLEX 460S (Tg: -28°C), SUPERFLEX 470 (Tg: -31°C), SUPERFLEX 500M (Tg: -39°C), SUPERFLEX 740 (Tg: -34°C), and SUPERFLEX 150HS (Tg: 32°C), all manufactured by DKS Co., Ltd.; DAOTAN TW6490 / 35WA (Tg: 32°C), manufactured by Daicel-Allnex Ltd.; TAK.ELAC W-6061 (Tg: 25°C), manufactured by Mitsui Chemicals, Inc.; and Ube Industries, all manufactured by DKS Co., Ltd. UW-1701F (Tg: 5℃) manufactured by Ltd and Sancure 777F manufactured by Lubrizol.

[0069] At least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin has a glass transition temperature (Tg) below 140°C and greater than or equal to 20°C. Furthermore, at least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin has a glass transition temperature (Tg) below 20°C. As is known to those skilled in the art, the glass transition temperature (Tg) is a value determined by differential scanning calorimetry (DSC).

[0070] The total amount of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin is 7%-10% by weight, thereby ensuring that the pigment is fixed onto the textile fabric without altering the fabric's feel. In this patent application, the weight percentages indicated for mixtures and water-dispersible resins refer to the amount of non-volatile water-dispersible resin in the inkjet ink formulation (i.e., calculated based on the solids or non-volatile content specified for a commercially available product). Preferably, the water-dispersible resin with a Tg below 20°C is present in the formulation in a total amount of 0.25%-1.5% by weight. Also preferably, a water-dispersible resin with a Tg below 140°C and greater than or equal to 20°C is present in the formulation in an amount of 2%-4% by weight.

[0071] Preferably, at least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin is subjected to a temperature of 25°C and a time of 200-400 seconds.-1 It has a viscosity of less than or equal to 600 cP (mPa·s) at a shear rate.

[0072] One preferred embodiment relates to an ink formulation in which the weight ratio of the pigment to the total amount of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin is 0.3 to 0.6. This ink formulation provides excellent rubbing fastness and color development properties to the printed textiles without affecting the hand feel of the textiles.

[0073] The inkjet ink contains up to 2% by weight of a surfactant. The term "surfactant" is known in the art. It specifically includes compounds that reduce surface tension and / or improve dispersion properties. Those skilled in the art can identify surfactants suitable for printable compositions produced by piezoelectric on-demand inkjet printing. The term includes cationic, anionic, nonionic, and amphoteric surfactants. Preferably, the surfactant is biodegradable and / or derived from renewable sources. Examples of suitable commercially available surfactants include, but are not limited to, rhamnolipids (e.g., REWOFERM® RL 100, a biosurfactant commercially available from Evonik), sophorolipids (e.g., REWOFERM® SL ONE, a biosurfactant commercially available from Evonik), sorbitan monooleate (commercially available from Sigma Aldrich under the trade name Span® 80), polyethylene glycol sorbitan monooleate (e.g., commercially available from Sigma Aldrich under the trade name Tween® 80), sodium dioctyl sulfosuccinate, ethoxylated 2,4,7,9-tetramethyl-5-decyn-4,7-diol, and mixtures thereof (e.g., Surfinol® PSA 336, commercially available from Evonik, which is a blend of sodium dioctyl sulfosuccinate and ethoxylated 2,4,7,9-tetramethyl-5-decyn-4,7-diol).

[0074] The inkjet ink composition further comprises 20% to 40% by weight, preferably 20% to 30% by weight, and more preferably 20% to 25% by weight of 1,2,3-propanetriol. The 1,2,3-propanetriol used is preferably of plant origin, such as from soybean oil, coconut oil, palm oil, or corn oil. The specified amount of water-miscible 1,2,3-propanetriol ensures that the composition is stable over its shelf life (at least 12 months) and can be ejected by piezoelectric drop-on-demand inkjet printing because it prevents the ink from drying in the DOD piezoelectric inkjet head and the temperature rise in the channels of the inkjet head. Furthermore, the specified amount of 1,2,3-propanetriol promotes ink adhesion to the side of the fabric to be printed and prevents ink migration to the other side of the fabric and the resulting back-side staining.

[0075] The inkjet ink composition may further contain a pH adjuster and / or a biocide and / or a thickener and / or an additional water-miscible solvent.

[0076] Preferably, the inkjet ink formulation has a pH value of 5-9. This pH value depends on the intended use (e.g., softening, water repellency) and the stability conditions of the inkjet ink formulation, as well as the properties and effects obtained on the fabric. If desired, the inkjet ink formulation may further contain up to 0.5% by weight of a pH adjuster, preferably plant-derived. Preferably, the pH adjuster is selected from acetic acid, citric acid, ascorbic acid, malic acid, etc. Preferably, citric acid is used to adjust the pH value of the composition within a pH range of 5-7, while acetic acid is used to adjust the pH value of the composition within a pH range of 7-9.

[0077] The inkjet ink composition may contain up to 0.5% by weight of a biocide. This biocide prevents biological deterioration of textiles, helps prevent the spread of infectious diseases without frequent sterilization, and ensures the stability of the inkjet ink composition for at least 12 months. Any biocide conventionally used in the textile industry is suitable for the textile finishing compositions according to the present invention. Such biocides include, but are not limited to, 1,2-benzisothiazolin-3-one (commercially available from Zeneca Specialties in the form of a solution sold under the trade name Proxel GXL), organocopper compounds, organotin compounds, chlorophenols, silver-based microbial agents, and metal-based inorganic compounds such as zinc oxide, zinc salts, and copper salts.

[0078] The inkjet ink composition may contain up to 1.0% by weight of a thickener. As is known to those skilled in the art, a thickener is a substance that increases the viscosity of a liquid without substantially altering its other properties. Those skilled in the art are capable of adjusting the amount of thickener to obtain the desired viscosity for the textile finishing composition. Preferably, the thickener is a plant-derived polysaccharide (e.g., starch, plant gum) and a water-dispersible polyester resin, such as Vylonal MD-2000 (Tg: 67°C) manufactured by Toyobo. Examples of suitable polysaccharide thickeners include, but are not limited to, carob gum (also known as locust bean gum or carob gum, which contains at least 75% galactomannan), such as commercially available Carob EXC 25 from HEIQ, Switzerland, guar gum, carrageenan, and alginate. Advantageously, the thickener is commercially available and readily dispersible in water when mixed. In a preferred embodiment, if present, the thickener is a polysaccharide thickener. In another preferred embodiment, the inkjet ink composition is free of thickeners but may contain biocides and / or pH adjusters as described herein.

[0079] The inkjet ink composition may contain 1% to 15% by weight, preferably 5% to 12.5% ​​by weight, more preferably 7.5% to 10% by weight, of an additional water-miscible solvent, preferably selected from...

[0080] - Alcohols, such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1,3-propanediol, 1,3-butanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol and 2-methyl-2-propanol;

[0081] - Diols, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol monohydrate and tripropylene glycol dihydrate; glycerol;

[0082] - Diethylene glycol derivatives, such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, triethylene glycol monohexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether; and

[0083] - Its mixture.

[0084] In a preferred embodiment, the additional water-miscible solvent is selected from ethylene glycol, 1,2-propanediol, diethylene glycol, and mixtures thereof, more preferably a mixture of ethylene glycol and diethylene glycol, or a mixture of ethylene glycol, propylene glycol, and diethylene glycol.

[0085] Ink Group

[0086] A second aspect of the invention relates to an ink group comprising at least three blendable inks, wherein each ink in the ink group is an inkjet ink formulation according to the invention. The blendable ink may contain...

[0087] (i) Yellow inkjet ink formulation, cyan inkjet ink formulation, magenta inkjet ink formulation, optional black inkjet ink formulation, optional white ink; or

[0088] (ii) Yellow inkjet ink formulations, cyan inkjet ink formulations, magenta inkjet ink formulations, black inkjet ink formulations, orange inkjet ink formulations, and blue inkjet ink formulations; or

[0089] (iii) Yellow inkjet ink formulations, cyan inkjet ink formulations, magenta inkjet ink formulations, black inkjet ink formulations, orange inkjet ink formulations, blue inkjet ink formulations, violet inkjet ink formulations, and green inkjet ink formulations; or

[0090] (iv) Yellow inkjet ink formulations, cyan inkjet ink formulations, magenta inkjet ink formulations, black inkjet ink formulations, orange inkjet ink formulations, red inkjet ink formulations, blue inkjet ink formulations, violet inkjet ink formulations, and green inkjet ink formulations.

[0091] Manufacturing method

[0092] According to a third aspect of the invention, there is a method for manufacturing a printed, optionally finished textile fabric, the method comprising, preferably, the following steps:

[0093] a) Provide an uncolored textile fabric, wherein the fabric has not previously undergone pretreatment for inkjet printing;

[0094] b) Printing one or more inkjet formulations on one side of the fabric or on one or more areas of the fabric using piezoelectric on-demand inkjet printing, wherein at least one of the inkjet formulations is an inkjet ink formulation as described and claimed herein;

[0095] c) Optionally, piezoelectric on-demand inkjet printing of one or more inkjet formulations is performed on the other side of the fabric or on one or more areas of the other side, wherein at least one of the inkjet formulations is an inkjet ink formulation as described and claimed herein.

[0096] d) Drying the textile by exposing it to air at a temperature of about 120°C to about 140°C to provide a dried textile; and

[0097] e) Calender the textile fabric at a temperature of about 140°C to about 180°C for at least 10 seconds to provide an optional finished textile fabric for printing.

[0098] Advantageously, this manufacturing method eliminates the need for a pretreatment step of the textile fabric prior to printing step b) and / or a post-coating step of protecting the printed image with resin. Therefore, this manufacturing method is environmentally friendly in terms of water, chemical, and energy consumption, and provides printed, optionally finished textile fabrics exhibiting excellent rubbing fastness and color development properties in a time-saving manner compatible with the requirements of the textile industry.

[0099] As used herein, the term "textile fabric" is intended to encompass all forms of textile substrates, including woven, knitted, and nonwoven textile substrates. This term is intended to exclude fibrous substrates with two-dimensional rigidity, such as carpets, paper, and cardboard. Although sometimes referred to as textiles, these fibrous substrates are internally connected in a way that maintains a substantially fixed two-dimensional form. While they may be flexible in a third dimension, they generally cannot freely stretch or twist within the plane of the fiber layers, which is inherent to true textiles. Preferably, the textile is longer than 100 meters (e.g., 500 meters) and can be supplied on a roll with a width greater than 1 meter. Preferably, the textile is a woven, knitted, or nonwoven textile fabric. The fabric preferably comprises synthetic and / or natural fibers, preferably selected from silk fibers, cellulose fibers, elastic fibers, polyamide fibers, and polyester fibers. In some embodiments, the fabric may comprise animal-derived fibers, such as down, wool, leather, or fur.

[0100] The term "undyed textile fabric" refers to a fabric made from fibers that have not yet been in contact with a colorant.

[0101] The textile fabric provided in step a) has not undergone a pretreatment process for inkjet printing prior to this step. As is known to those skilled in the art of pigment inks for textile printing, this pretreatment process involves applying a pretreatment agent or coagulant (e.g., polyvalent metal salts and / or cationic polymers) to the textile fabric prior to the printing step (e.g., by impregnation, coating, or spraying). This pretreatment agent reacts with the components of the applied ink, particularly with the pigments and resins contained in the ink. Pretreatment agents or coagulants are well known in the art and include those described in US 2014 / 0210900 A1 and US 2019 / 0352528 A1.

[0102] In step b) of the method described and claimed herein, one or more inkjet formulations are applied to the surface of the textile fabric or one or more areas of the surface of the textile fabric by piezoelectric on-demand inkjet printing. At least one of the inkjet formulations is an inkjet ink formulation according to the invention. Advantageously, the use of piezoelectric on-demand inkjet printing enables the selective deposition of one or more inkjet ink formulations on one or more areas (sites) of the surface of the textile fabric or the surface of the substrate.

[0103] As is well known in the art, the term "face" refers to the front or back of a textile.

[0104] The manufacturing method described and claimed herein optionally includes step c), wherein one or more inkjet formulations are applied to the other side of the fabric or to one or more areas of the other side by piezoelectric on-demand inkjet printing. At least one of the inkjet formulations is an inkjet ink formulation according to the invention.

[0105] Conveniently, the manufacturing method described and claimed herein enables the simultaneous application of multiple inkjet formulations to an area (part) of a textile using a single piezoelectric on-demand inkjet printhead. Preferably, in steps b) and / or c) of the method of the invention, at least two, preferably at least three, more preferably at least four (e.g., five, six, seven, eight, nine, or ten) different inkjet formulations are applied using a single piezoelectric on-demand inkjet printhead. The wet deposits of these at least two, preferably at least three, more preferably at least one inkjet formulation may be the same or different.

[0106] In one embodiment, one or more of the inkjet formulations applied in steps b) and / or c) are textile finishing compositions. The term "textile finishing composition" refers to a ready-to-use, water-based, colorless composition that can be printed by piezoelectric on-demand inkjet printing and contains one or more finishing agents (i.e., substances that modify the properties of textiles other than color). The term "textile finishing composition" does not include compositions used in the post-coating process for images printed using pigment inks with a resin layer protection without colorants. Particularly suitable compositions are described in pending patent application number PCT / EP2023 / 085415.

[0107] In step d) of this method, the textile fabric obtained in step b) or c) is subjected to drying to evaporate the water contained in the textile finishing composition and provide a dried textile. This step is achieved by exposing the printed textile to air at a temperature of about 120°C to about 140°C. The exposure time depends on the surface density (g / m³) of the deposited inkjet formulation. 2The time and temperature used are preferably less than 3 minutes, more preferably less than 2 minutes, very preferably about 1 minute, and meet the speed requirements of industrial manufacturing methods for textiles.

[0108] The dried textile is then calendered at a temperature of about 140°C to about 180°C for at least 10 seconds, preferably about 30 seconds, to provide a printable, optionally finished textile fabric. Preferably, the calendering of the dried textile is less than 60 seconds. The pressure of the calender can be adjusted between 0 and 6 bar so that the rollers of the calender contact the dried textile. Preferably, the pressure applied during the calendering step is 2 to 4 bar. This step ensures that the pigment, and if present, the finishing agent, is fixed to the textile fibers.

[0109] In one embodiment, the method according to the invention includes steps a), b), c), d), and e), preferably consisting of steps a), b), c), d), and e).

[0110] Preferably, steps a), b), d), and e), or a), b), c), d), and e), of the method described herein and claimed are performed sequentially. In this embodiment, units for continuously feeding textiles, piezoelectric on-demand inkjet printing, drying, and fixing are installed sequentially to each other, and the textiles move continuously through them. The units for steps a), b), d), and e), or a), b), c), d), and e), may also be combined in a single machine. The textiles are continuously conveyed through the machine and are in a finished state when they leave the machine.

[0111] This method can be performed using commercially available industrial textile printing presses (such as the Panthera D8 or Panthera S4 from Swiss Performance Chemicals; or the LaRIO from MS Printing Solutions) or the EFI Reggiani HYPER and calender (rotary hot press rolls) from Reggiani.

[0112] A printing speed of approximately 50 m / min can be achieved using the methods described herein and claimed.

[0113] The optionally finished textile fabric for printing can be an indigo-free fabric with the visual appearance of denim. In this case, in step b) of the method described herein and claimed, a parallel straight-line pattern is printed on one side of the fabric or in an area of ​​said side of the fabric to provide the visual appearance of the back of denim, wherein said side of the fabric is the back of the fabric; and

[0114] In step c), a pattern is printed on the other side of the fabric or on an area of ​​said other side of the fabric to provide the visual appearance of the right side of the denim, wherein said other side of the fabric is the right side of the fabric. Preferably, the distance between every two adjacent lines is 0.1mm-5mm, and the line has a width of 0.1mm-2mm; and / or

[0115] The textile fabric is a woven fabric with a diagonal rib, and the parallel straight lines are printed at an angle of 60°-120° to the rib.

[0116] This document also describes and claims a method for manufacturing garments, including the steps of transforming the printed, optionally finished textile fabric into garments. The garments may be, for example, jeans, jackets, shirts, skirts, dresses, or scarves.

[0117] use

[0118] According to a fourth aspect of the invention, therein lies the use of the inkjet ink formulation or ink group thereof for printing textile fabrics. Detailed Implementation

[0119] Example

[0120] To further illustrate the present invention, the following embodiments are provided. These embodiments are not intended to limit the scope of the invention.

[0121] Table 1: Ingredients

[0122]

[0123] I. Preparation of Pigment Dispersions

[0124] The following four dispersions, CMYK, were prepared by mixing the materials shown in Table 2.

[0125] Table 2: CMYK dispersion of the composition

[0126]

[0127] II. Preparation of Ink Formulation

[0128] Starting with the CMYK dispersion shown in Table 2, the following eight ink formulations were prepared by mixing the dispersion with the materials shown in Table 3 for 4 hours. The resulting mixtures were microfiltered to provide CMYK ink. Viscometer BROOKFLIED DVN (flat cone, 50 RPM) was used at 25°C for 200 s. -1 Viscosity was measured at a certain shear rate.

[0129] Table 3: Formulation of CMYK Ink Compositions

[0130]

[0131] 1 The weight ratio of pigment to the total amount (non-volatile content) of water-dispersible (meth)acrylic resin, water-dispersible styrene-(meth)acrylic resin and water-dispersible polyurethane resin.

[0132] Preparation of printed textile fabrics

[0133] Printed using piezoelectric on-demand inkjet printing (using a Panthera S4 machine from Swiss Performance Chemicals AG; printing resolution 600x600 dpi, 2 passes; printing speed 250m). 2 / h; wet sedimentation rate: 6-12g / m³ 2 CMYK ink is printed onto the surface of a textile fabric. The printed textile is dried by exposing it to hot air (120-140°C) for 90 seconds. Subsequently, the dried textile is calendered at 140°C and an average pressure of 3 bar for 30 seconds to provide the printed textile fabric.

[0134] The following fabrics were tested:

[0135] White 100% cotton satin 120g / m 2

[0136] White 100% Cotton (Toile Popline) 130g / m 2

[0137] White cotton / PES 80 / 20% Toilet 135g / m 2

[0138] White 100% PES Natté 210g / m 2

[0139] The fabric was not pretreated for inkjet printing before the printing step.

[0140] III. Performance Evaluation of Printed Textiles

[0141] The textile hand, color development, dry rubbing fastness, wet rubbing fastness, and backstaining of the prepared printed textile fabrics were evaluated using the methods described below. Results obtained using inks C2, M2, Y2, and K2 on a 100% cotton satin substrate are summarized in Table 4. Similar or better results were obtained for the other three test substrates.

[0142] Textile feel

[0143] Experts in this field compared the original textile fabric (i.e., the textile fabric before printing) with the printed textile fabric obtained as described in Section III.

[0144] The evaluation criteria for changes in the hand feel of textiles are as follows:

[0145] The feel of the textile fabric remains unchanged;

[0146] The feel of the textile fabric changes slightly;

[0147] The feel of textile fabrics has changed significantly (stiffness).

[0148] Color development

[0149] Color rendering is evaluated by measuring optical density (OD) using a colorimeter, with 100% as the reference for maximum color saturation. The following standards are used to evaluate color rendering:

[0150] 100% OD value;

[0151] 98-100% OD value;

[0152] OD value below 98%.

[0153] Dry rubbing fastness & wet rubbing fastness

[0154] The rubbing fastness of indicator pigments to the adhesion quality of textile fabrics is evaluated using a rubbing fastness tester.

[0155] Specifically, the printed fabric sample was rubbed with a white 100% cotton rubbing cloth under a specified pressure (9 Newtons) by making the fabric reciprocate in a straight line. To test the wet rubbing fastness (wet rubbing fastness), a wet white 100% cotton rubbing cloth was used. Due to mechanical abrasion, some of the pigment was transferred from the printed textile fabric to the rubbing cloth, causing discoloration of the printed textile fabric. Color intensity was evaluated using a five-point scale (called a grayscale scale). Level (or grade) 1 is the lowest value, and level 5 is the best value. At level 5, the color of the cotton rubbing cloth showed no change.

[0156] Back dyed

[0157] Back-side dyeing is evaluated by measuring the optical density (OD) values ​​of the printed side (front) and the back side of the textile fabric using a colorimeter. The following standards are used to evaluate back-side dyeing:

[0158] The back side has a very low color depth compared to the front side (the measured OD of the back side is less than 3% of the measured OD of the front side).

[0159] The back side has a lower color density compared to the front side (the measured OD of the back side is 3%-5% of the measured OD of the front side).

[0160] The color is visible on the back (the measured OD on the back is 5% higher than the measured OD on the front).

[0161] Table 4: Performance of Printed 100% Cotton Satin Substrate

[0162]

Claims

1. Formulation of silicone-free and fluorine-free water-based piezoelectric on-demand inkjet inks for textile printing. The formulation is prepared at 25°C for 200-400 seconds. -1 It has a viscosity of 4 mPa·s to 9 mPa·s, preferably 4-7 mPa·s, at a shear rate, and is composed of the following: - 3% to 15.0% by weight of pigment dispersed in the formulation; - Water-dispersible (meth)acrylic resins; - Water-dispersible styrene-(meth)acrylic resins; - Water-dispersible polyurethane resin; - Up to 2% by weight of surfactant; - 20% to 40% by weight of 1,2,3-propanetriol; - Optionally, at least one of a pH adjuster, a biocide, a thickener, and another water-miscible solvent; and - water; in At least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin has a glass transition temperature (Tg) of less than 140°C and greater than or equal to 20°C. At least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin has a glass transition temperature (Tg) below 20°C; and The total amount of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin and the water-dispersible polyurethane resin is 7% to 10% by weight. The percentage by weight is based on the total weight of the composition.

2. The inkjet ink formulation according to claim 1, wherein at least one of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin, and the water-dispersible polyurethane resin is at 25°C and 200-400s. -1 It has a viscosity of less than or equal to 600 mPa·s at a shear rate.

3. The inkjet ink formulation according to claim 1 or 2, wherein the weight ratio of the pigment to the total amount of the water-dispersible (meth)acrylic resin, the water-dispersible styrene-(meth)acrylic resin and the water-dispersible polyurethane resin is 0.3 to 0.

6.

4. The inkjet ink formulation according to any one of the preceding claims, wherein the formulation does not contain a thickener.

5. The inkjet ink formulation according to any one of the preceding claims, wherein the formulation comprises 1%-15% by weight, preferably 5%-12.5% ​​by weight, more preferably 7.5%-10% by weight, of an additional water-miscible solvent and / or the water-miscible solvent is selected from ethylene glycol, propylene glycol, diethylene glycol and mixtures thereof.

6. An ink group comprising at least three blendable inks, wherein each ink in the ink group is an inkjet ink formulation according to any one of claims 1-5.

7. A method for manufacturing an optional finished textile fabric for printing, the method comprising, preferably, the following steps: a) Provide an uncolored textile fabric, wherein the fabric has not previously undergone pretreatment for inkjet printing; b) Printing one or more inkjet formulations on one side of the fabric or on one or more areas of the fabric using piezoelectric on-demand inkjet printing, wherein at least one of the inkjet formulations is an inkjet ink formulation according to any of the preceding claims. c) Optionally, piezoelectric on-demand inkjet printing of one or more inkjet formulations is performed on the other side of the fabric or on one or more regions of the other side, wherein at least one of the inkjet formulations is an inkjet ink formulation according to any of the preceding claims. d) Drying the textile by exposing it to air at a temperature of about 120°C to about 140°C to provide a dried textile; and e) Calender the textile fabric at a temperature of about 140°C to about 180°C for at least 10 seconds to provide an optional finished textile fabric for printing.

8. The method of claim 7, wherein the method comprises steps a), b), c), d), and e), preferably consisting of steps a), b), c), d), and e).

9. The method according to any one of the preceding claims, wherein the textile fabric comprises synthetic and / or natural fibers, preferably selected from silk fibers, cellulose fibers, elastic fibers, polyamide fibers and polyester fibers.

10. The method according to any of the preceding claims, wherein steps a), b), c), d), and e) are performed sequentially.

11. The method according to any of the preceding claims, wherein in steps b) and / or c), at least two, preferably at least three, more preferably at least four inkjet formulations are printed using a single piezoelectric on-demand inkjet printhead.

12. The method according to any one of the preceding claims, wherein one or more of the inkjet formulations are textile finishing compositions, preferably wherein the textile finishing composition is selected from textile softening compositions, water-repellent textile finishing compositions, and textile finishing compositions for improving wicking properties.

13. The method according to any one of the preceding claims, wherein the optionally finished textile fabric of the print is an indigo-free fabric having the visual appearance of denim, and wherein... In step b), a parallel straight line pattern is printed on one side of the fabric or on a region of said side of the fabric to provide the visual appearance of the back of the denim, wherein said side of the fabric is the back of the fabric. and In step c), a pattern is printed on the other side of the fabric or on an area of ​​the other side of the fabric to provide the visual appearance of the front side of the denim, wherein the other side of the fabric is the front side of the fabric.

14. The method of claim 13, wherein the distance between any two adjacent lines is 0.1 mm to 5 mm, and the line has a width of 0.1 mm to 2 mm; and / or The fabric is a woven fabric with a diagonal rib pattern, and the parallel straight lines are printed at an angle of 60°-120° to the rib.

15. A method of manufacturing garments, comprising the step of converting a printed, optionally finished textile fabric according to any one of claims 7-14 into garments.

16. Use of the inkjet ink formulation according to any one of claims 1-5 or the ink group according to claim 6 for printing textile fabrics.

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